KR20070034527A - Release Laminated Film - Google Patents

Abstract

A layer made of a modified polyolefin resin having surface characteristics of a fluororesin, which is less likely to cause delamination, has excellent workability and economy, and can easily follow the stepped shape of the multilayer substrate when press-molded again; The release film which has a layer which consists of adhesive fluororesin laminated | stacked on at least one side of this layer is provided.

Adhesive fluororesin, modified polyolefin resin, interlayer peeling, workability, release film for release.

Description

Release laminated film {Mold releasing laminated film}

TECHNICAL FIELD This invention relates to the laminated | multilayer film for mold release which has a layer which consists of a fluororesin on the surface, and especially relates to the laminated | multilayer film for mold release used suitably for the press molding of a multilayer board | substrate.

A release film means the film for forming a coating film on the said film by apply | coating and hardening various adhesive materials, coating materials, etc. on the said film, and making it possible to peel and use such a coating film.

Conventionally, as these release films, fluororesin films, such as Teflon (PTFE) (PTFE), a poly (4-methylpentene-1) film, the film which apply | coated the silicone type material to biaxially stretched polyethylene terephthalate (PET) surface layer, etc. Is being used. In particular, a film using a fluororesin for the surface layer is known to be extremely low in adhesion and excellent in releasability. For example, Patent Document 1 proposes to use a fluorine resin film as a release film. In addition, Patent Document 2 proposes to use a film laminated on a thermoplastic resin with a surface layer as a fluorine-based resin as a release film.

In addition, the release film is used for printing substrates, ceramic electronic components, thermosetting resins,

When manufacturing a makeup plate etc., it may be used, sandwiching between metal plates or between resin so that metal plates or resin may not adhere | attach during a process.

For example, in the manufacture of a substrate for printing, a method of generally superimposing several sheets of prepregs impregnated with an epoxy resin into a glass fiber fabric, then loading metal foil such as copper foil, and heating and pressing a press machine to integrate them. Although this is performed, it prevents sticking to each other through a release film between the press board of a press working machine, a board | substrate for printing, and the said board | substrates, in this way.

In particular, with the recent increase in the density of printed boards, the construction of surface mounts has also changed, and multilayer boards having stepped irregularities have been used to load surface mount parts such as chips. In the case of laminating and molding a multilayer substrate having such a shape, it is difficult to apply pressure uniformly to the molded object in a conventional molding method, so that a method of embedding silicon rubber or the like in a stepped portion and applying pressure while heating is performed. It is carried out. Moreover, in order to apply pressure uniformly, shaping | molding by the vacuum multistage lamination apparatus is also proposed.

In addition, in order to prevent the prepreg resin inserted between the layers of the multi-layer substrate during the press molding from melting and flowing out into the cavity portion, Patent Document 3 has a three-layer structure, and the upper and lower two layers are heat-resistant resins such as fluorine resin, The multilayer film for laminated presses which the core layer was formed from thermoplastic resins, such as polyethylene, is disclosed. In such a multilayer film, when pressed, the intermediate layer is in a melt pressurized state, whereby prepreg can be prevented from flowing out.

Patent Document 1: Japanese Patent Application Laid-Open No. 8-186141

Patent Document 2: Japanese Unexamined Patent Publication No. 2002-208782

Patent document 3: Unexamined-Japanese-Patent No. 10-296765

Disclosure of the Invention

Problems to be Solved by the Invention

However, in patent document 1 and patent document 2, since a fluororesin film is expensive, there exists a problem from the point of cost to put into practical use as a release film. In addition, if a thin fluororesin film is used to solve the cost problem, there is a problem that the elasticity of the film is lost, the handling property is inferior, or thermal adhesion with a stainless steel sheet occurs during the production of a printing substrate.

Moreover, in the laminated body which uses a surface layer as a fluororesin like patent document 2, since the adhesiveness of a fluororesin is low, the adhesive force with a non-fluorine-type thermoplastic resin etc. is weak, and there exists a problem of being easy to produce interlayer peeling.

Moreover, the multilayer film disclosed by patent document 3 needs to adhere | attach the fluororesin layer of a top and bottom two layers, and the polyethylene resin layer which is a core layer. When bonding a fluororesin layer and a polyethylene resin layer, the method of dry lamination is employ | adopted normally. When the method of dry lamination is taken, in order to adhere | attach without interposing a bubble etc., it is necessary to have a predetermined | prescribed thickness on both layers to stick. This is connected with the use of a large amount of expensive fluorine-based resins, and there is a problem that causes a cost increase of the multilayer film raw material.

In addition, the dry lamination itself which prepares each layer separately, and attaches these layers is an effort | work effort, and is causing a raise in manufacturing cost. Moreover, since each layer has a thickness more than a predetermined | prescribed, there exists also a problem that a multilayer film cannot follow the step shape of a multilayer substrate well at the time of press molding.

Therefore, the present invention has a surface characteristic of a fluorine resin, and it is difficult to produce interlaminar peeling, is excellent in workability and economical efficiency, and can be easily followed by a stepped shape of a multilayer substrate when press molding again. Let it be a subject to provide a film.

Means to solve the problem

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated. In addition, in order to make an understanding of this invention easy, the reference numeral of an accompanying drawing is written in parentheses, but this invention is not limited to the form shown by this.

The first invention is a release laminated film 100A having a layer 10 made of a modified polyolefin resin and a layer 20 made of an adhesive fluororesin laminated on at least one side of the layer.

In the first aspect of the invention, it is preferable that the layers 20a and 20b made of an adhesive fluororesin are laminated on both sides of the layer 10 made of a modified polyolefin resin.

In the first aspect of the present invention, the thickness of the layer 20 made of an adhesive fluororesin is 1 to 15 μm, and the thickness of the layer 10 made of a modified polyolefin resin is preferably 10 to 100 μm.

In the second aspect of the present invention, at least one surface of the layer 30 made of a polyolefin resin, a layer 10 made of a modified polyolefin resin and a layer 20 made of an adhesive fluorine resin are laminated in this order ( 100C).

In the second invention, the layers 10a and 10b made of the modified polyolefin resin and the layers 20a and 20b made of the adhesive fluorine resin are laminated on both sides of the layer 30 made of the polyolefin resin in this order. desirable.

In the second invention, the thickness of the layer 20 made of an adhesive fluorine resin is 1 to 15 μm, and the thickness of the layer 10 made of a modified polyolefin resin is 0.5 to 100 μm and the layer 30 made of polyolefin resin. It is preferable that the thickness is 10-100 micrometers.

In a third aspect of the present invention, a release laminated film in which a layer 20 made of an adhesive fluorine resin and a layer 40 made of a fluorine resin are laminated in this order on at least one side of the layer 10 made of a modified polyolefin resin ( 100E).

In the third aspect of the present invention, layers 20a and 20b made of an adhesive fluororesin and layers 40a and 40b made of a fluororesin are laminated on both sides of the layer 10 made of a modified polyolefin resin in this order. desirable.

In the third aspect of the present invention, the thickness of the layer 40 made of fluorine resin is 1 to 15 μm, the thickness of layer 20 made of adhesive fluorine resin is 0.5 to 15 μm, and the thickness of the layer 10 made of modified polyolefin resin. It is preferable that the thickness is 10-100 micrometers.

In the fourth aspect of the present invention, at least one side of the layer 30 made of a polyolefin resin includes a layer 10 made of a modified polyolefin resin, a layer made of an adhesive fluororesin, and a layer made of a fluorine resin. It is the laminated | multilayer film for release 100G laminated in order.

In the fourth aspect of the present invention, layers 10a and 10b made of modified polyolefin resin, layers 20a and 20b made of adhesive fluorine resin and layers 40a made of fluorine resin are formed on both sides of layer 30 made of polyolefin resin. , 40b) is preferably laminated in this order.

In the fourth aspect of the present invention, the thickness of the layer 40 made of fluorine resin is 1 to 15 μm, the thickness of layer 20 made of adhesive fluorine resin is 0.5 to 15 μm, and the thickness of the layer made of modified polyolefin resin (10 ), The thickness of the layer 30 made of 0.5 to 100 µm and polyolefin resin is preferably 10 to 100 µm.

It is preferable that the modified polyolefin resin which forms the layer 10 which consists of modified polyolefin resin in 1st-4th this invention is a modified polyethylene resin.

In the third and fourth inventions, the fluorine resin forming the layer 40 made of the fluorine resin is preferably an ethylene-tetrafluoroethylene copolymer.

The fifth aspect of the present invention is a laminated film for release having a layer made of a heat resistant resin and a layer made of a fluororesin laminated on at least one side of the layer.

In the fifth aspect of the present invention, it is preferable that a layer made of a fluororesin is laminated on both surfaces of the layer made of a heat resistant resin.

In the fifth aspect of the present invention, the thickness of the layer made of fluorine resin is preferably 1 to 15 µm and the thickness of the layer made of heat resistant resin is 10 to 150 µm.

In the fifth aspect of the present invention, the fluorine resin forming the layer of the fluorine resin is preferably an ethylene-tetrafluoroethylene copolymer, a low melting point ethylene-tetrafluoroethylene copolymer, or a mixture thereof.

It is preferable that the heat resistant resin which forms the layer which consists of a heat resistant resin in 5th this invention is any of a polycarbonate, ethylene-vinyl alcohol copolymer, and polyamide.

A sixth aspect of the present invention is a laminate film disposed between a press plate and such a laminate when a laminate press formed by heating a laminate formed by superimposing a plurality of substrates via an adhesive, the core layer 50a and such a core layer. A laminate film having layers 20a and 20b made of an adhesive fluororesin laminated on both sides of a film, wherein the core layer 50a is formed of a resin having a melting point lower than that of the adhesive fluororesin (100J). )to be.

In the sixth present invention, the core layer 50a is preferably a layer made of a modified polyolefin resin.

In the sixth aspect of the present invention, one selected from the group consisting of a modified polyolefin resin, an ethylene-vinyl alcohol copolymer (EVOH) and a polyamide between the layers 20a and 20b made of an adhesive fluorine resin and the core layer 50a. It is preferable to have the intermediate | middle layers 60a and 60b which consist of the above thermoplastic resins.

In the sixth invention, the modified polyolefin resin is preferably a modified polyethylene.

In the sixth aspect of the present invention, the thicknesses of the layers 20a and 20b made of the adhesive fluororesin are preferably 5 to 20 m.

In a sixth aspect of the present invention, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoro are placed on the outer side of the layers 20a and 20b of the adhesive fluorine resin. Ethylene-perfluoroalkylvinylether copolymer (PFA), polychlorotrifluoroethylene (CTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride and It is preferable to have layers 70a and 70b made of a fluorine resin made of at least one resin selected from the group consisting of acid-modified ETFE (EFEP).

In the sixth invention, the thickness of the entire film is preferably 100 to 1200 µm.

In the first to sixth inventions, the release laminated film 100 is preferably formed by coextrusion.

Effects of the Invention

According to the present invention, there is provided a releasing laminated film for release of a fluororesin that is excellent in mold release property, hardly exfoliates, has excellent workability and economy, and can easily follow a stepped shape of a multilayer substrate when press molding again. Can provide.

Best Mode for Carrying Out the Invention

<First Embodiment>

The layer structure of the laminated | multilayer film for mold release of this invention is shown in FIG. As shown in Fig. 1 (a), the release laminated film 100A of the present invention comprises a layer 10 made of a modified polyolefin resin and a layer 20 made of an adhesive fluorine resin laminated on at least one side of the layer. Have

In the present invention, the "adhesive fluororesin" has a melting point of 150 ° C to 250 ° C and a sample pressure of Rexpearl RA3150 (manufactured by Nippon Polyethylene), which is one of modified polyolefin resins, and a fluorine resin of 4x10 ⁵ to 5x10 ⁵ Pa. Pressed at 240 ° C. for 10 minutes to produce a laminated sheet, and cut a sample cut into a width of 2.5 cm and a length of 25 cm by a method according to JIS Z0237 at a peeling rate of 5 mm / min and a temperature of 23 ° C., 180 degrees. When measuring peeling strength, the thing of fluororesin whose 180 degree peeling strength is 4 N / cm or more is said.

In the present invention, the IR spectrum of the "adhesive fluororesin" has an absorption peak between 1780 cm ^-1 and 1880 cm ^-1 . Preferably, IR spectrum of the "adhesive fluoropolymer" is 1790cm ^-1 to 1800cm ^-1 and 1845cm ^-1 to 1855cm between of an absorption peak due to acid anhydride such as maleic anhydride, or between ^-1, 1800cm ^-1 1815cm ^-1 to have an absorption peak attributable terminal carbonate groups or between, such as 1790cm ^-1 to 1800cm ^-1 among 1845cm ^-1 to 1855cm ^-1 and 1800cm between maleic acid anhydride and between ^-1 to 1815cm ^-1 It has an absorption peak resulting from the mixture of terminal carbonate groups.

More preferably, IR spectrum of the "adhesive fluoropolymer" is 1790cm ^-1 to 1800cm ^-1 and 1845cm ^-1 to 1855cm between of an absorption peak due to acid anhydride such as maleic anhydride, or between ^-1, 1800cm ^{- It} has an absorption peak attributable to the terminal carbonate group between ¹ and 1815 cm ^-1 .

Incidentally, the ratio of the height at the vicinity of 2881cm ^-1 due to CH ₂ groups in the main chain absorption between 1790cm ^-1 to 1800cm ^-1 peak resulting from the anhydride, such as for the height of the absorption peak, maleic acid is 0.5 to 1.5, Preferably it is 0.7-1.2, More preferably, it is 0.8-1.0.

In addition, the absorption of the height of a peak between about the height of the absorption peak of 2881cm ^-1 in the vicinity resulting from groups of the main chain CH _2, 1800cm ^-1 to 1815cm ^-1 due to the terminal carbonate groups ratio of 1.0 to 2.0, preferably 1.2 to 1.8, more preferably 1.5 to 1.7.

Examples of the fluororesin having such an adhesive strength include homopolymers and copolymers having tetrafluoroethylene units, and functional groups such as carbonate groups, carboxylic acid halide groups, hydroxyl groups, carboxyl groups, and epoxy groups at the terminal or side chain thereof. Resin which has is mentioned. A plurality of resins can be mixed as long as the melting point and the adhesive strength are expressed. As a fluorine resin which has the above-mentioned adhesive strength as a commercial item, Neoflon EFEP (made by Daikin Kogyo Co., Ltd.) and Pluon LM-ETFE AH2000 (made by Asahi Glass Corporation) are mentioned, for example.

In the present invention, the term "modified polyolefin resin" refers to a polyolefin resin based on

The resin obtained by graft-reacting an acid, such as an inorganic acid, unsaturated carboxylic acid, or its derivative (s) by arbitrary methods is mentioned. As a base polyolefin, polyethylene, a polypropylene, etc. are used, for example. As unsaturated carboxylic acids, boronic acid, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, these acid anhydrides, ester, amide, imide, metal salt, etc. are used, for example. As the modified polyolefin resin, a copolymer of ethylene and glycidyl methacrylate is preferable. As a copolymer of such ethylene and glycidyl methacrylate, Rexpearl RA3150 (made by Nippon Polyethylene) and Bondfast E (made by Sumitomo Chemical Co., Ltd.) are mentioned, for example.

The release laminated film 100A of the present invention may further laminate several layers 90 as needed on the layer 10 made of such a modified polyolefin resin. Among them, as shown in Fig. 1 (b), the configuration 100B in which the layers 20a and 20b made of adhesive fluorine resin are laminated on both sides of the layer 10 made of modified polyolefin resin is shown on both sides. It is preferable at the point which can exhibit mold release property and is excellent also in economy.

When configured as the release laminated films 100A and 100B shown in FIGS. 1A and 1B, the layers 20, 20a, and 20b made of an adhesive fluorine resin have a thickness of 1 to 15 µm and a modified polyolefin resin. It is preferable that the layer 10 consists of 10-100 micrometers. By constituting in this way, even if the layers 20, 20a, and 20b made of adhesive fluororesin are thin, the layer 10 made of modified polyolefin resin has an appropriate thickness and rigidity. It can be set as laminated | multilayer film 100A, 100B. In addition, since the expensive adhesive fluororesin is used only in the minimum necessary amount, it is also excellent in economy.

As shown in FIG. 1 (c), the release laminated film 100 of the present invention comprises a layer 10 made of a modified polyolefin resin and an adhesive fluorine resin on at least one side of the layer 30 made of a polyolefin resin. The layer 20 can be the laminated | multilayer film 100C laminated | stacked in this order.

Examples of the polyolefin resin used for the layer 30 made of the polyolefin resin include polyethylene and polypropylene. Of these, polyethylene is preferable in view of cushioning and sealing properties at the time of pressing. When comprised in this way, in laminated | multilayer film 100A, 100B, in order to make workability favorable, only the layer 10 which consists of modified polyolefin is made to have thickness, or in laminated | multilayer film 100C, the layer which consists of polyolefin resin more inexpensive 30 ), It is possible to have a thickness, it is possible to reduce the amount of use of the modified polyolefin resin, it can be set to a release laminated film (100C) excellent in economic efficiency.

Also in the laminated film 100C for release which provided the layer 30 which consists of polyolefin resin, several layers 90 can be laminated further as needed. Among them, as shown in Fig. 1 (d), layers 10a and 10b made of modified polyolefin resin and layers 20a and 20b made of adhesive fluorine resin on both sides of the layer 30 made of polyolefin resin. It is preferable to set it as the laminated | multilayer film for release 100D laminated | stacked in this order. By setting it as such a structure, mold release property can be exhibited on both surfaces, and it can also be made excellent in economic efficiency.

1 (c) and 1 (d), when configured as the release laminated film (100C, 100D), the layer of the adhesive fluorine resin (20, 20a, 20b) is 1 to 15㎛, modified polyolefin resin It is preferable that the layers 10, 10a, and 10b are made of 0.5 to 100 m, and the layer 30 made of a polyolefin resin is 10 to 100 m. By constituting in this way, even if the layers 20, 20a, and 20b made of the adhesive fluororesin are thin, the layer 30 made of the polyolefin resin can have an appropriate thickness, so that the release layer having excellent elasticity and workability is excellent. It can be set as the film 100C, 100D. In addition, since the expensive adhesive fluororesin is used only in the minimum necessary amount, it is also excellent in economy.

The other structure of the laminated | multilayer film for mold release of this invention is shown in FIG. As shown in FIG. 2 (a), the release laminated film 100 of the present invention is formed of a layer 20 made of an adhesive fluorine resin and a fluorine resin on at least one side of a layer 10 made of a modified polyolefin resin. The layer 40 can be made into the release laminated film 100E in which these layers are laminated | stacked.

Examples of the fluorine resin used for the layer 40 made of the fluorine resin include ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), and tetrafluoroethylene-hexafluoropropylene air. Copolymer (FEP), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), and the like. Among these, ETFE is preferable in terms of mold release property, workability, and the like. ETFE can be easily obtained as a commercial item, For example, aflon COP (made by Asahi Glass Co., Ltd.), Tcfzel (made by Dupont Co., Ltd.), Neoflon ETFE (made by Daikin Kogyo Co., Ltd.), etc. are mentioned.

In the release film 100E for release, since the outermost layer has the layer 40 which consists of fluororesins, compared with the case where the layer 20 which consists of adhesive fluororesins is in outermost layer, it is especially high temperature (200 degreeC or more). The releasability in the case of using it for press molding of is excellent. It is considered that the adhesive fluorine resin exhibits adhesion performance when the adhesive fluorine resin is more than its melting point, and the releasability tends to be lowered, whereas the conventional fluorine resin is low in adhesiveness at high temperatures.

As shown in FIG. 2A, the release laminated film 100E of the present invention may further laminate several layers 90 as necessary on the layer 10 made of such a modified polyolefin resin. Among them, as shown in Fig. 2 (b), the layers 20a and 20b made of adhesive fluorine resin and the layers 40a and 40b made of fluorine resin on both sides of the layer 10 made of modified polyolefin resin. It is preferable to set it as the laminated film for release 100F of the structure laminated | stacked in this order. In such a laminated film 100F, the releasability can be exhibited from both sides, and the economical efficiency can be made excellent.

When composed of the release film 100E or 100F shown in FIGS. 2A and 2B, the layers 40, 40a, and 40b made of fluororesin are 1 to 15 µm, and an adhesive fluorine resin. It is preferable that the layer 20 which consists of 20, 20a, and 20b is 0.5-15 micrometers, and the layer 10 which consists of modified polyolefin resin is 10-100 micrometers. By constituting in this way, even if the layers 40, 40a and 40b made of fluororesin are thin, the layer 10 made of modified polyolefin resin can have appropriate thickness and rigidity. It can be set as laminated | multilayer film 100E, 100F. In addition, since the expensive fluorine resin uses only the minimum required amount, it is also excellent in economic efficiency.

As shown in FIG. 2 (c), the release laminated film 100 of the present invention includes a layer 10 made of a modified polyolefin resin and an adhesive fluorine resin on at least one side of the layer 30 made of a polyolefin resin. The layer 20 and the layer 40 which consist of a fluororesin can be set as the release laminated film 100G in which these layers are laminated | stacked in this order.

When comprised in this way, in order to improve workability in release laminated films 100E and 100F, only the layer 10 which consists of a modified polyolefin resin is made, or in the laminated film 100G for release, it is more inexpensive made of polyolefin resin. Since the thickness can be made also by the layer 30, the usage-amount of a modified polyolefin resin can be reduced and it can be set as the release laminated film 100G which is more economical.

Similarly to the release laminated film 100E, some layers 90 may be further laminated in the release laminated film 100G as needed. Of these, the layers 10a and 10b made of modified polyolefin resin and the layer made of adhesive fluorine resin on both sides of the layer 30 made of polyolefin resin, such as the release laminated film 100H shown in FIG. 2 (d). It is preferable to set it as the release laminated film 100H in which the layers 40a and 40b which consist of (20a, 20b) and the fluororesin are laminated | stacked in this order. By setting it as such a structure, mold release property can be exhibited on both surfaces, and it can also be made excellent in economic efficiency.

When configured in the same manner as the release laminated film 100G or the release laminated film 100H, the layers 40, 40a and 40b made of fluorine resin are 1 to 15 µm and the layers 20, 20a and 20b made of adhesive fluorine resin. Is 0.5 to 15 µm, and the layers 10, 10a and 10b made of the modified polyolefin resin are 0.5 to 100 µm and the layer 30 made of the polyolefin resin is preferably 10 to 100 µm. By constructing in this way, even if the layers 40, 40a, and 40b made of fluorine resin are thin, the layer 30 made of polyolefin resin has an appropriate thickness, so that the release laminated film having excellent elasticity and workability can be obtained. have. In addition, since the expensive fluorine resin uses only the minimum required amount, it is also excellent in economic efficiency.

<2nd embodiment>

The release laminated film 100 of this invention can be set as the structure which has a layer which consists of a heat resistant resin, and the layer which consists of a fluororesin laminated | stacked on at least one surface of this layer. In particular, the invention according to the second embodiment is a release laminated film that can be suitably used even in a high temperature environment.

In addition, several layers can be laminated | stacked again as needed on the surface on the opposite side with the surface which laminated | stacked the layer which consists of fluororesins in the layer which consists of said heat resistant resin. Among these, it is preferable to set it as the structure by which the layer which consists of a fluororesin are laminated | stacked on both surfaces of the layer which consists of heat resistant resins from the point which can exhibit mold release property on both surfaces and is excellent in economic efficiency.

Here, it is preferable that the thickness of the layer which consists of fluororesins is 1-15 micrometers, and it is preferable that the thickness of the layer which consists of heat resistant resins is 10-150 micrometers. By configuring in this way, even if the layer which consists of fluororesins is thin, since it can make a layer which consists of heat resistant resins suitable thickness and rigidity, it can be set as the release laminated film excellent in elastic workability. In addition, since the expensive fluorine resin uses only the minimum required amount, it is also excellent in economy.

In the second embodiment, the fluorine resin forming the layer made of the fluorine resin is preferably an ethylene-tetrafluoroethylene copolymer, a low melting point ethylene-tetrafluoroethylene copolymer or a mixture thereof.

Here, the low melting point ethylene-tetrafluoroethylene copolymer is an adhesive fluorine resin whose definition is described in the first embodiment.

As a heat resistant resin which forms the layer which consists of heat resistant resins, a polycarbonate, a polycarbonate-type alloy, a polyetherimide, an ethylene-vinyl alcohol copolymer, a polyamide, and a polyamide-type alloy are mentioned. Among these, it is preferable to use polycarbonate, ethylene-vinyl alcohol copolymer, and polyamide.

By forming the layer which consists of heat resistant resins with these resins, it can be set as the mold release laminated film excellent in heat resistance at low cost. In addition, these resins can be molded by coextrusion. This can solve the problem of inclusion of foreign matter between the layers as in the case of laminating a PET film.

At high temperatures (eg, 180 ° C. or higher), the modulus of elasticity of the above-mentioned heat-resistant resin decreases, but the end portion of the release-laminated film is blown off with an ultrasonic welder, or the like to be used at the end portion as shown in FIG. By bonding the layer made of a fluororesin, the above-mentioned problems of softening and dissolving of the resin can be solved.

Moreover, even if the laminated | multilayer film for mold release of this embodiment cut | disconnects a film with a blade, it has close adhesiveness between layers of the grade which does not peel. In addition, when attaching a tape to a release laminated film and providing a tension part, each layer can be isolate | separated by having such a tension part and peeling easily a release laminated film. Thus, the release laminated film of the present invention has the advantage that each layer can be peeled off and separated after use, and can be disposed of separately.

Third Embodiment

3: (a) is sectional drawing of the thickness direction which shows the laminated constitution of the laminated | multilayer film 100J for release according to 3rd Embodiment of this invention. The illustrated laminated film 100J has a three-layer structure, and layers 20a and 20b made of an adhesive fluororesin are disposed on both sides of the core layer 50a. In this embodiment, it is essential that resin which comprises the core layer 50a is resin whose melting | fusing point is lower than adhesive fluororesin. By taking such a configuration, only the resin constituting the core layer 50a can be melted by heating during press molding, and it can easily follow the stepped shape of the multilayer substrate during press molding. At the distal end of the laminated film 100J, as shown on the left side of Fig. 3 (a), the layers 20a and 20b made of two layers of adhesive fluororesin are directly bonded to seal the core layer 50a. Although it is preferable to take the structure, the laminated film 100J is sufficiently thin in comparison with its surface area, and in general, the size of the laminated film 100J is larger than the surface in contact with the mold, so that the sealing structure is not essential.

Although the kind of resin which comprises the core layer 50a is not specifically limited, Melting | fusing point of the adhesive fluororesin which can obtain adhesion | attachment with the layers 20a and 20b which consist of an adhesive fluororesin easily can also be obtained. In view of having a lower melting point, it is preferably at least one thermoplastic resin selected from the group consisting of modified polyolefin resins, ethylene-vinyl alcohol copolymers (EVOH) and polyamides.

In this embodiment, "modified polyolefin resin" and "adhesive fluororesin" are the same as those in 1st Embodiment.

In the laminated | multilayer film 100J which concerns on this embodiment, the layers 20a and 20b which consist of two layers of adhesive fluororesins are arrange | positioned so that the core layer 50a may be pinched | interposed in a laminated constitution. Therefore, no adhesive is required to bond between the core layer 50a and the layers 20a and 20b made of an adhesive fluororesin. In this manner, when producing the laminated film 100J according to the present embodiment, it is not necessary to go through the dry lamination process as in the prior art, and the laminated film 100J can be formed at once by coextrusion. In addition, since the film can be produced by coextrusion, a layer made of an expensive adhesive fluororesin can be thinned as a raw material.

In the laminated film 100J which concerns on this embodiment, although the thickness of the layers 20a and 20b which consist of adhesive fluororesins is not specifically limited, It is preferable to exist in the range of 5-20 micrometers. If the thickness of the layers 20a and 20b made of the adhesive fluorine resin is too thin, there is a possibility that a problem may occur in terms of strength. If the thickness of the layers 20a and 20b made of the adhesive fluorine resin is made thicker than this, the raw material cost rises and the advantage of producing the laminated film 100J by coextrusion is lost. In addition, the thicknesses of the layers 20a and 20b made of two layers of adhesive fluororesin may be the same and may be different.

On the other hand, since the layers 20a and 20b made of adhesive fluorine resin are formed thin in the above range, the flexibility of the laminated film 100J when the resin of the core layer 50a is melted increases, so that the multilayer substrate is subjected to the laminated press. It is easy to follow the step-shaped shape of, and it can prevent that the prepreg resin inserted between the layers of a multilayer board | substrate melts and flows out into a cavity part at the time of press molding.

The total thickness of the laminated film 100J according to this embodiment is not particularly limited. The yaw should be in the range of the thickness filled without gaps as far as possible between layers of the multilayer substrate when deformed by heating of press molding, and from this point of view, the thickness is preferably 100 to 1200 mu m.

As shown in Fig. 3 (b), the release laminated film 100 of the present embodiment is a modified polyolefin and ethylene-vinyl alcohol again between the layers 20a and 20b made of an adhesive fluorine resin and the core layer 50b. It can be set as the release laminated film 100K which has the intermediate | middle layers 60a and 60b which consist of one or more thermoplastic resins chosen from the group which consists of a copolymer (EVOH) and a polyamide. In this embodiment, it is essential that resin which comprises the core layer 50b is resin which has melting | fusing point lower than melting | fusing point of resin which comprises layers 20a and 20b which consist of adhesive fluororesin. By taking such a configuration, only the resin constituting the core layer 50b can be melted by the heating during press molding, and it can easily follow the stepped shape of the multilayer substrate during press molding. At the distal end of the laminated film 100K, as shown on the left side of FIG. 3 (b), the intermediate layers 60a and 60b are preferably bonded directly to take the structure of sealing the core layer 50, but the laminated film 100K is sufficiently thin in comparison with its surface area, and since the size of the laminated film 100K is usually larger than the surface in contact with the mold, the sealing structure is not essential.

In the present embodiment, the resin constituting the intermediate layers 60a and 60b preferably has good adhesiveness with the resin constituting the layers 20a and 20b made of the adhesive fluorine resin, and from this viewpoint, the intermediate layers 60a and 60b are used. The resin constituting the resin is preferably at least one thermoplastic resin selected from the group consisting of a modified polyolefin, an ethylene-vinyl alcohol copolymer (EVOH) and a polyamide.

Although the kind of resin which comprises the core layer 50b is not specifically limited in the laminated | multilayer film 100K of this embodiment, It is preferable to have favorable adhesiveness between resin which comprises the intermediate | middle layers 60a, 60b. . In the case where the above preferred thermoplastic resin is used as the intermediate layers 60a and 60b, the adhesion between the core layer 50b and the intermediate layers 60a and 60b is achieved by the layers 20a and 20b made of the core layer 50b and the adhesive fluororesin. It is easier than when bonding. Moreover, polyethylene, a polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, etc. can be used preferably from a viewpoint of having melting | fusing point lower than melting | fusing point of the adhesive fluorine resin available.

In the laminated film 100K according to the present embodiment, two intermediate layers 60a and 60b are disposed to sandwich the core layer 50b during the layer configuration, and the adhesive fluorine resin is disposed on the outside of the intermediate layers 60a and 60b. The layers 20a and 20b which consist of are arrange | positioned. That is, the intermediate layers 60a and 60b are disposed between the core layer 50b and the layers 20a and 20b made of an adhesive fluororesin to achieve adhesion between both layers. Thus, no adhesive is required between both layers. In this way, when producing the laminated film 100K according to the present embodiment, it is not necessary to go through the dry lamination process as in the prior art, and the laminated film 100K having a five-layer structure can be formed at once by coextrusion. . In addition, since film production by co-extrusion can be performed, the layers 20a and 20b made of an expensive adhesive fluororesin can be made thin as a raw material.

In addition, in the laminated film 100K according to the present embodiment, the intermediate layers 60a and 60b are left to adhere to the layers 20a and 20b made of an adhesive fluorine resin, and the core layer 50b is made of an adhesive fluorine resin. It can select only from a viewpoint of having melting | fusing point lower than melting | fusing point of resin which comprises (20a, 20b). Therefore, the width | variety of selection of resin which comprises the core layer 50b can be taken widely. In this way, it is easy to reduce the raw material cost and to impart a new function to the laminated film 100K.

In the laminated film 100K according to the present embodiment, the thickness of the layers 20a and 20b made of the adhesive fluororesin is not particularly limited, but is preferably in the range of 5 to 20 µm. If the thickness of the layers 20a and 20b made of the adhesive fluorine resin is too thin, there is a concern that a problem may occur in terms of strength. If the thickness of the layers 20a and 20b made of the adhesive fluorine resin is made thicker than this, the raw material cost rises and the advantage of producing the laminated film 100K by coextrusion is lost. In addition, the thicknesses of the layers 20a and 20b made of two layers of adhesive fluororesin may be the same and may be different.

In the laminated | multilayer film 100K which concerns on this embodiment, although the thickness of the intermediate | middle layers 60a and 60b is not specifically limited, It is preferable to exist in the range of 1-20 micrometers. It is difficult to manufacture the thickness of the intermediate layers 60a and 60b by coextrusion. On the contrary, when thickness is thicker than this, raw material cost rises and the advantage of manufacturing laminated | multilayer film 100K by coextrusion is lost. In addition, the thicknesses of the intermediate layers 60a and 60b of the two layers may be the same and may be different.

Thus, by forming the layers 20a and 20b made of the adhesive fluorine resin and the intermediate layers 60a and 60b as described above, the flexibility of the laminated film 100K is increased when the resin of the core layer 50b is melted. Therefore, it is easy to follow the stepped shape of the multilayer substrate at the time of lamination press, and it is possible to prevent the prepreg resin inserted between the layers of the multilayer substrate at the time of press molding from melting and flowing out into the cavity portion.

The total thickness of the upper film 100K according to the present embodiment is not particularly limited. The yaw is good if it is a range of thickness which fills without gap as much as possible between layers of a multilayer substrate when it deforms by heating of press molding, and it is preferable that it is 100-1200 micrometers in thickness from this viewpoint.

As shown in FIG.3 (c), in the laminated film 100 for releases of this embodiment,

On the other side of layers 20a and 20b made of adhesive fluororesin, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl Vinyl ether copolymer (PFA), polychlorotrifluoroethylene (CTFE), ethylene-tetrafluoroethylene copolymer (ETFE), low melting point ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride ( PVDF), polyvinyl fluoride and acid-modified ETFE (EFEP) can be configured to have layers 70a and 70b made of a fluorine resin composed of at least one resin selected from the group consisting of: Here, low melting point ethylene-tetrafluoroethylene copolymer (ETFE) is resin which has a low melting point among ETFE, for example, Fluon LM720 by Asahi Glass Co., Ltd. is mentioned.

By adopting such a configuration, the peelability, gas barrier properties, and non-transferability of impurities from the laminated film 100L to the multilayer substrate side in the press-molding of the laminated film 100L to the multilayer substrate are further improved.

When the layers 70a and 70b made of fluororesin are provided as the outer layer, the thicknesses of the outer layers 70a and 70b may be the same and may be different. Moreover, it is preferable that the thickness is 5-20 micrometers. If the thickness of the outer layer is too thin, there is a fear that problems occur in terms of strength. In addition, if the thickness of the outer layer is too thick, the cost of the raw material rises, the advantage of producing the laminated film 100L by coextrusion is lost.

<Method of Manufacturing Laminated Film 100 for Release>

Although the lamination | stacking method of the lamination | stacking release film 100 which concerns on said 1st Embodiment-3rd embodiment is mentioned, a heat-sealing press, co-extrusion, etc. are mentioned, Among these, the laminated film for release release 100 desired by multilayer coextrusion is mentioned. ) Is produced at once from the viewpoint of productivity and cost. Moreover, a co-extrusion and a press can be combined and the laminated film which improved the adhesiveness between films can be produced.

<Use of Release Laminated Film 100>

The release laminated film 100 of the present invention according to the first to third embodiments described above forms a coating film on the film by applying and curing various adhesive materials, paints, and the like on the film, and peeling the coating film. It is used as a film for release so that it may be used. In addition, the release laminated film (100B, 100D, 100F, 100H, 100J, 100K, 100L) of the form which laminated | stacked the layer which consists of adhesive fluororesins or the layer which consists of fluororesins on both surfaces of the intermediate | middle layer 10 is demonstrated below. It is also used as the release film 100 used for the press molding of the laminated body for multilayer board | substrates.

Hereinafter, the case where the release laminated film 100 which concerns on 3rd Embodiment is used about the laminated press molding of a multilayer board | substrate is demonstrated as an example. The release laminated film 100 of this invention is used in order to suppress the outflow of adhesive resin at the time of carrying out lamination | stacking press by overlapping several board | substrate through an adhesive bond layer. The release laminated film 100 of the present invention is disposed and used in the laminated press molding apparatus 200 as shown in FIG. 4 (a).

The laminated press-molding apparatus 200 is equipped with the hot plates 220a and 220b for press which are attached to the front-end | tip of hydraulic cylinder 210a, 210b, and are arrange | positioned so that it may face up and down. 4: (a) is a vertical sectional drawing which shows typically the state before a press, and several board | substrates 230, 230, ... are mounted on the lower press hotplate 220b. A prepreg is inserted in between the board | substrates 230, 230, .... Prepreg impregnates resin in core materials, such as glass fiber.

As resin for prepreg, epoxy resin, BT resin, phenol resin, unsaturated polyester resin, vinyl ester resin, polyimide resin, polyphenylene oxide resin, fluorine resin, polyethylene terephthalate resin, polybutylene terephthalate resin, di And thermosetting resins such as allyl phthalate resins alone or mixtures or modified substances thereof. Among them, epoxy resins and BT resins are preferably used in terms of heat resistance reliability. These resins may contain inorganic fillers such as talc, clay, silica and calcium carbonate, and fibrous fillers such as glass fibers, asbestos fibers and ceramic fibers as necessary. The resin for prepreg is dissolved in a predetermined solvent and impregnated into a core material to form a prepreg. As the core material of the prepreg, although glass fiber is common, aromatic polyamide fiber can be used besides this. Moreover, mat-shaped glass, polyester, and aromatic polyamide can be used. In addition, the resin amount of a prepreg is 30 to 80 weight% normally with respect to the whole prepreg.

Lamination press molding of the laminate for multilayer substrates is usually carried out at a temperature of 160 to 280 ° C. At this time, the core layers 50a and 50b made of thermoplastic resin are in a molten state, while the layers 20a and 20b made of adhesive fluorine resin sandwiching the core layers 50a and 50b are in a softened state. Here, the "molten state" of the core layers 50a and 50b includes a state in which, in addition to the liquid state, it is easily deformed by press pressure and sufficiently softened so that the concave-convex portion of the molding can be buried substantially without gaps. do. In addition, "softening" of the layers 20a and 20b made of an adhesive fluororesin is such that the shape according to the unevenness of the molding is easily given by the internal pressure of the molten resin of the core layers 50a and 50b during press molding. It means to be softened. Therefore, when pressurized by the upper and lower press hot plates 220a and 220b, the molten resin of the core layers 50a and 50b is closed and pressurized in the space surrounded by the layers 20a and 20b made of adhesive fluorine resin. The layers 20a and 20b made of an adhesive fluororesin are given a shape corresponding to the unevenness of the molding by the internal pressure of the molten resin of the core layers 50a and 50b (Fig. 4 (b)). As a result, the space formed by the stepped cavity portion and the hot plates 220a and 220b for press is buried by the molten resin of the core layers 50a and 50b under pressure. Since the pressure of such molten resin is equal to or higher than the pressure of the adhesive to flow out between the substrates, the outflow of the prepreg resin between the multi-layered substrates to be molded can be suppressed. The pressure of the molten resin is determined by the relationship between the volume of the cavity portion and the thickness of the layers 20a and 20b made of the adhesive fluororesin. That is, the pressure of molten resin is determined by the magnitude relationship of the volume of molten resin of core layer 50a, 50b, and the volume of a stepped cavity part. The higher the pressure, the greater the effect of suppressing the outflow of the prepreg resin.

<Production (1) of laminated film for release>

(Example 1)

Coextrusion is carried out in a multi-manifold die at 280 ° C. to obtain the following configuration, to obtain the desired film.

1-layer adhesive fluorocarbon resin (Neoplon EFEP EP-5000 manufactured by Daikin Kogyo Co., Ltd.) 10 μm

2nd layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene Co., Ltd.) 80 μm

3rd layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 10 μm

(Example 2)

According to the same method as in Example 1 to obtain the following configuration to obtain the desired film.

1-layer adhesive fluorocarbon resin (Neoplon EFEP EP-5000 manufactured by Daikin Kogyo Co., Ltd.) 10 μm

10-micrometer of 2nd layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene)

3rd layer polyolefin resin (Novatech HD HJ580 by Nippon Polychem Co., Ltd.) 60 μm

Four-layer modified polyolefin resin (Rexpearl RA3150 made by Nippon Polyethylene) 10 μm

Fifth Layer Adhesive Fluorine Resin (Neoplon EFEP EP-5000, manufactured by Daikin Kogyo Co., Ltd.) 10 μm

(Example 3)

Co-extruded in a multi-manifold die at 280 ° C to achieve the following configuration, and press-treated at 240 ° C for 10 minutes at a pressure of 5 x 10 ^-3 Pa (5 kgf / cm ² ) to obtain the desired film.

First layer adhesive fluororesin (neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 5 μm

2 layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene) 5 micrometers

3rd layer polyolefin resin (Novatec HD HJ580 manufactured by Nippon Polychem Co., Ltd.) 60 μm

4 layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene) 5 micrometers

5th layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 5 μm

(Example 4)

A laminated film for release was obtained in the same manner as in Example 1 except that Fluon LM-ETFE AH2000 manufactured by Asahi Glass Co., Ltd. was used as the adhesive fluorine resin.

(Example 5)

A laminated film for release was obtained in the same manner as in Example 2 except that Fluon LM-ETFE AH2000 manufactured by Asahi Glass Co., Ltd. was used as the adhesive fluorine resin.

(Example 6)

A laminated film for release was obtained in the same manner as in Example 3 except that Fluon LM-ETFE AH2000 manufactured by Asahi Glass Co., Ltd. was used as the adhesive fluorine resin.

(Comparative Example 1)

A laminated film for release was obtained in the same manner as in Example 1 except that the first layer and the third layer of Example 1 were used as tetrafluoroethylene-hexafluoropropylenevinylidene fluoride copolymer (THV220G manufactured by Dion). .

(Comparative Example 2)

A laminated film for release was obtained in the same manner as in Example 1 except that the first layer and the third layer of Example 1 were used as a tetrafluoroethylene-hexafluoropropylene copolymer (Neoplon FEP manufactured by Daikin Corporation).

(Comparative Example 3)

A laminated film for release was obtained in the same manner as in Example 1 except that the first layer and the third layer of Example 1 were made of vinylidene fluoride (KF polymer T # 850 manufactured by Creha Co., Ltd.).

(Example 7)

Coextrusion is carried out in a multi-manifold die at 280 ° C. to obtain the following configuration, to obtain the desired film.

First layer fluorine resin (fluon ETFE C-88AXP made by Asahi Glass Corporation) 5 micrometers

2nd layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 10 μm

3 layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene Co., Ltd.) 40 micrometers

4th layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 10 μm

5th layer fluorocarbon resin (fluon ETFE C-88AXP made by Asahi Glass Corporation) 5 micrometers

(Example 8)

Coextruded in a multi-manifold die at 280 ℃ to achieve the following configuration, and press-treated at 240 ℃ for 10 minutes at a pressure of 5 × 10 ^-3 Pa (5 kgf / cm ² ), to obtain the desired film.

First layer fluorine resin (fluon ETFE C-88AXP made by Asahi Glass Corporation) 5 micrometers

2nd layer adhesive fluororesin (neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 5 micrometers

3 layer modified polyolefin resin (Rexpearl RA3150 made by Nippon Polyethylene Co., Ltd.) 80 μm

4th layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 5 μm

5th layer fluorocarbon resin (fluon ETFE C-88AXP made by Asahi Glass Corporation) 5 micrometers

(Example 9)

The desired film was obtained in the same manner as in Example 7 so as to have the following configuration.

First layer fluorine resin (fluon ETFE C-88AXP made by Asahi Glass Corporation) 5 micrometers

2nd layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 10 μm

10-micrometer of 3rd layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene)

4 layer polyolefin resin (Novatec HD HJ580 by Nippon Polychem Co., Ltd.) 70 μm

5th layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene) 10 micrometers

6th layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 10 μm

The seventh layer fluorine resin (fluon ETFE C-88AXP made from Asahi Glass Corporation) 5 micrometers

(Example 10)

The desired film was obtained in the same manner as in Example 8 so as to have the following configuration.

First layer fluorine resin (fluon ETFE C-88AXP made by Asahi Glass Corporation) 5 micrometers

2nd layer adhesive fluororesin (neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 5 micrometers

3 layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene) 5 micrometers

4 layer polyolefin resin (Novatec HD HJ580 by Nippon Polychem Co., Ltd.) 70 μm

5th layer modified polyolefin resin (Rexpearl RA3150 by Nippon Polyethylene) 5 micrometers

6th layer adhesive fluororesin (Neoplon EFEP EP-5000 by Daikin Kogyo Co., Ltd.) 5 μm

The seventh layer fluorine resin (fluon ETFE C-88AXP made from Asahi Glass Corporation) 5 micrometers

(Example 11)

A laminated film for release was obtained in the same manner as in Example 7 except that Fluon LM-ETFE AH2000 manufactured by Asahi Glass Co., Ltd. was used as the adhesive fluorine resin.

(Example 12)

A laminated film for release was obtained in the same manner as in Example 8 except that Fluon LM-ETFE AH2000 manufactured by Asahi Glass Co., Ltd. was used as the adhesive fluorine resin.

(Example 13)

A laminated film for release was obtained in the same manner as in Example 9 except that Fluon LM-ETFE AH2000 manufactured by Asahi Glass Co., Ltd. was used as the adhesive fluorine resin.

(Example 14)

A laminated film for release was obtained in the same manner as in Example 10 except that Fluon LM-ETFE AH2000 manufactured by Asahi Glass Co., Ltd. was used as the adhesive fluorine resin.

(Comparative Example 4)

A laminated film for release was obtained in the same manner as in Example 7 except that the second layer and the fourth layer of Example 7 were made of polyethylene resin (Novatech HD HJ580 manufactured by Nippon Polychem Co., Ltd.).

(Comparative Example 5)

A laminated film for release was obtained in the same manner as in Example 7 except that the second layer and the fourth layer of Example 7 were tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV220G manufactured by Dion). do.

(Comparative Example 6)

A laminated film for release was obtained in the same manner as in Example 7 except that the second layer and the fourth layer of Example 7 were made a tetrafluoroethylene-hexafluoropropylene copolymer (Neopleon FEP manufactured by Daikin Corporation).

(Comparative Example 7)

A laminated film for release was obtained in the same manner as in Example 7 except that the second layer and the fourth layer of Example 7 were made of vinylidene fluoride (KF polymer T # 850 manufactured by Creha).

(Comparative Example 8)

A 50-micrometer-thick ETFE (Fluon ETFE C-88AXP made by Asahi Glass Co., Ltd.) film is used as it is.

<Lamination Press Molding (1) of Substrate>

The films produced in the above Examples 1 to 14 and Comparative Examples 1 to 8 are used as release films in substrate molding for printing. The film was sequentially pressed from the lower layer to the press working machine for forming a substrate for printing. Glass cloth-injected prepreg) / release film / stainless steel (SUS) decorative plate / cushion material].

<Evaluation method (1)>

The film produced by said Example 1-14 and Comparative Examples 1-8 and the film used for laminated press molding are evaluated by the following evaluation items. The evaluation results are summarized in Table 1 and Table 2.

(Extrusion Processability)

0: A film can be obtained stably by co-extrusion (coextrusion + press in some cases).

X: When coextrusion, it peels between layers and does not wind up stably.

(Layer adhesion)

0: No interlayer peeling occurs.

X: Interlayer peeling arises at the time of winding-up.

(Sealing)

Visually check that the epoxy resin does not emerge from the through hole of the printing substrate.

0: Resin does not blow out from the through hole.

(Triangle | delta): It is within 0.5 mm that resin blows out from a through hole.

X: It is 0.5 mm or more that resin blows out from a through hole.

(Surface release)

After press working, it is visually evaluated whether there is releasability between the stainless steel (SUS) decorative plate and the laminated molding material.

0: There is release property and it peels off slightly.

X: There is no release property and it cannot be used.

(Workability)

The ease of handling of the laminated | multilayer film for release at the time of application | coating or a press is evaluated.

0: The film is elastic, easy to fix and wrinkles are not tangled.

X: It is not elasticity to a film, hard to fix, and wrinkles are easy to be entangled.

Extrusion processability Interlayer adhesive Sealability Surface release Workability Example 1 O O O O O Example 2 O O O O O Example 3 O O O O O Example 4 O O O O O Example 5 O O O O O Example 6 O O O O O Comparative Example 1 O × - - - Comparative Example 2 O × - - - Comparative Example 3 O × - - -

As shown in Table 1, the laminated | multilayer film for releases (Examples 1-6) of this invention are favorable in the interlayer adhesiveness of a film, and are excellent in sealing property, surface mold release property, and workability as a release film. On the other hand, the laminated | multilayer film of Comparative Examples 1-3 is bad in interlayer adhesiveness, each layer peels and it cannot evaluate as a release film.

Extrusion processability Interlayer adhesive Sealability Surface release Economics Workability Example 7 O O O O O O Example 8 O O O O O O Example 9 O O O O O O Example 10 O O O O O O Example 11 O O O O O O Example 12 O O O O O O Example 13 O O O O O O Example 14 O O O O O O Comparative Example 4 O × O O O × Comparative Example 5 O △ O O O O Comparative Example 6 × × O O O × Comparative Example 7 O × O O O × Comparative Example 8 - - △ O × ×

From Table 2, it turned out that the laminated film for release (Examples 7-14) of this invention is excellent in the whole surface, such as interlayer adhesiveness and mold release property. On the other hand, although the film of Comparative Examples 4-7 is excellent in releasability, sealing property, and economics, it falls in any other item. Moreover, although using an ETFE film as it is (comparative example 8) is excellent in mold release property, it is inferior to economy and workability.

<Production (2) of laminated film for release>

(Example 15)

Coextrusion at a multi-manifold die at 300 ° C. to obtain the following configuration yields the desired film.

First layer fluorine resin (Tefgel 290, manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.) 5 μm

2nd layer heat resistant resin (Yupiron S-2000, manufactured by Mitsubishi Engineering Plastics, Inc.) 100 μm

3 layer fluorocarbon resin (Tefgel 290 by Mitsui Dupont Fluorochemical Co., Ltd.) 5 μm

(Example 16)

A release film was obtained in the same manner as in Example 15 except that Neoflon EFEP RP-5000 manufactured by Daikin Industries Co., Ltd. was used as the fluorine resin.

(Example 17)

A release film was obtained in the same manner as in Example 15 except that Nihon GE Plastic Ultem 1000 was used as the heat resistant resin.

(Example 18)

Coextrusion at a multi-manifold die at 300 ° C. to obtain the following configuration yields the desired film.

First layer fluorine resin (Tefgel 290, manufactured by Mitsui DuPont Fluoro Chemical Co., Ltd.) 5 μm

2nd layer heat resistant resin (Yupiron S-2000, manufactured by Mitsubishi Engineering Plastics, Inc.) 100 μm

3 layer fluorocarbon resin (Tefgel 290 by Mitsui Dupont Fluorochemical Co., Ltd.) 5 μm

(Example 19)

A release film was obtained in the same manner as in Example 18 except that Neoflon EFEP RP-5000 manufactured by Daikin Industries, Ltd. was used as the fluorine resin.

(Example 20)

As a heat resistant resin, the release film was obtained like Example 18 except having used Ultem 1000 by Nippon GE Plastics.

(Example 21)

A release film was obtained in the same manner as in Example 18 except that UBE Nylon 6 1015B manufactured by Ubegosan Co., Ltd. was used as the heat resistant resin.

(Example 22)

As a heat resistant resin, the release film was obtained like Example 18 except having used Sonolol A4412 by Kosei Chemical Co., Ltd., Japan.

(Example 23)

A release film was obtained in the same manner as in Example 15 except that THV220 manufactured by Sumitomos Rem Corporation was used as the fluorine resin.

(Example 24)

A release film was obtained in the same manner as in Example 15 except that Neoflon FEP manufactured by Daikin Industries Co., Ltd. was used as the fluorine resin.

(Comparative Example 9)

A 50-micrometer-thick ETFE (Fluon ETFE C-88AXP made by Asahi Glass Co., Ltd.) film is used as it is.

(Example 25)

A release film was obtained in the same manner as in Example 18 except that THV220 manufactured by Sumitomos Rem Corporation was used as the fluorine resin.

(Example 26)

A release film was obtained in the same manner as in Example 18 except that Neoflon FEP manufactured by Daikin Industries Co., Ltd. was used as the fluorine resin.

(Comparative Example 10)

A 50-micrometer-thick ETFE (Fluon ETFE C-88AXP made by Asahi Glass Co., Ltd.) film is used as it is.

(Reference Example 1)

The film of Example 1 is used.

<Lamination Press Molding (2) of Substrate>

Performance evaluation is carried out by using the films produced in the above Examples 15 to 26, Comparative Examples 9 to 10 and Reference Example 1 as release films in substrate molding for printing. The film is sequentially pressed from the lower layer to the press working machine for forming a substrate for printing. ) / Release film / stainless steel (SUS) makeup plate / cushion material], and the press is performed under the conditions of a press pressure of 3.6 MPa, a press temperature of 180 ° C., and a heating time of 77 minutes.

<Evaluation method (2)>

The film produced by said Example 15-26, Comparative Examples 9-10, and Reference Example 1, and the film used by laminated press molding are evaluated by the following evaluation items. The evaluation results are summarized in Table 3.

(Extrusion Processability)

0: A film can be obtained stably by coextrusion.

(Triangle | delta): Although coextrusion is possible, peeling is seen at the time of winding up.

X: It peels between layers at the time of coextrusion, and does not wind up stably.

(Layer adhesion)

0: When cutting with a blade and bending a cut part with a finger once, interlayer peeling does not arise.

(Triangle | delta): An interlayer peeling arises when cut | disconnecting with a blade and bending a cut part with a finger once.

X: When cutting with a blade, interlayer peeling occurs.

(Sealing)

Visually check that the epoxy resin does not emerge from the through hole of the printing substrate.

0: Resin does not blow out from the through hole.

(Triangle | delta): It is within 0.5 mm that resin blows out from a through hole.

X: It is 0.5 mm or more that resin blows out from a through hole.

(High temperature sealability)

It evaluates similarly to said "sealing property" except having changed heating temperature from 180 degreeC to 200 degreeC in laminated press molding.

(Surface release)

After press working, visual evaluation is performed to see if there is releasability between the stainless steel (SUS) decorative plate and the laminated molding material.

0: There is release property and it peels off slightly.

(Triangle | delta): Although there exists mold release property, there exists a part which is hard to peel off.

X: There is no release property and it cannot be used.

(Workability)

The ease of handling of the laminated | multilayer film for release at the time of application | coating or a press is evaluated.

0: The film has elasticity, is easy to fix, and wrinkles are not entangled.

(Triangle | delta): The elasticity of a film is weak, and wrinkles tend to be entangled at the time of fixing.

X: A film does not have elasticity, and it is hard to fix it, and wrinkles are easy to be entangled.

Extrusion processability Interlayer adhesive Sealability High temperature sealability Surface release Workability Example 15 O O O O O O Example 16 O O O O O O Example 17 O O O O O O Example 18 O O O O O O Example 19 O O O O O O Example 20 O O O O O O Example 21 O O O O O O Example 22 O O O O O O Example 23 O O O O △ △ Example 24 △ △ O O O O Comparative Example 9 - - △ O O × Example 25 O O O O △ △ Example 26 △ △ O O O O Comparative Example 10 - - △ O O × Reference Example 1 O O O △ O O

<Production of Release Laminated Film and Upper Layer Press Forming of Substrate (3)>

(Example 27)

The board | substrate which produced the laminated body used for the multilayer board | substrate for BGA (Ball Grid Array) using the laminated film 100 for release of this invention impregnated BT resin [brand name: HL830 (made by Mitsubishi Gas Chemical Co., Ltd.)] on the glass base material. Use what you have. In addition, the thing which impregnated BT resin (brand name: HL830 (made by Mitsubishi Gas Chemical Co., Ltd.)) to the glass core material is used for a prepreg. The amount of resin is 75%.

The release laminated film 100 used in this embodiment is a film in the form of (100L) shown in Fig. 3 (c). The laminated film 100 is obtained by coextrusion in a multi-manifold die at 240 ° C. When explaining each layer of the laminated | multilayer film 100, the layers 70a and 70b which consist of fluororesins form ETFE (brand name: Pluon LM720; the product made by Asahi Glass Co., Ltd.) at 2.5 micrometers in thickness. Adhesive layer The layer 20a, 20b which consists of a fluororesin and Neoflon EFEP EP-5000 by Daikin Industries Co., Ltd. is formed in thickness of 2.5 micrometers. In addition, the core layer 50a forms modified polyethylene (trade name: Rexpearl RA3150; manufactured by Nippon Polyethylene) at a thickness of 500 µm. Moreover, melting | fusing point of ETFE is 230 degreeC, and melting | fusing point of adhesive fluororesin is 200 degreeC.

Lamination press molding is performed as follows. As shown in FIG. 5, three sheets of stainless steel plates 320a and 320b, cushioning material (not shown), and substrates are used between the molds 310a and 310b which are disposed to face each other above and below the press-molding apparatus 300. As shown in FIG. Substrate 330a, 330b, 330c, prepreg 340a, 340b, and the release laminated film 100 are arrange | positioned. That is, in the release film 100 for releasing, a layer made of fluorine resin (for example, 70a) is in contact with the lower surface side of the stainless steel plate 320a, and a layer made of fluorine resin (for example, 70b) is placed on the upper surface side of the substrate 330a. It is arranged to contact. The pin hole is provided here, respectively, and this pin hole is inserted into the positioning pin 350 provided between the metal molds 310a and 310b, and is positioned.

The stainless steel plates 320a and 320b use SUS630 stainless steel. The press pressure is 0.98 MPa and 1.96 MPa in two stages of pressurization. The molding temperature is 200 ° C., and the pressure is changed from 0.98 MPa to 1.96 MPa when the temperature is 110 ° C. during the temperature increase. The holding time of 200 degreeC shall be 5 minutes. Press molding is carried out under such molding conditions, and after completion of molding, the laminate is taken out. When the obtained laminated body was observed with the electron microscope, the outflow of prepreg is not confirmed.

(Comparative Example 11)

A laminate for multilayer substrates was produced in the same manner as in Example 27 except that the laminate was molded without using a release film. When observed with an electron microscope, the outflow of prepreg was confirmed by the uneven surface of the obtained laminated body.

FIG. 1: is a schematic diagram which shows the laminated constitution of the laminated | multilayer film for mold release of 1st Embodiment.

It is a schematic diagram which shows the laminated constitution of the laminated | multilayer film for mold release of 1st Embodiment.

It is a schematic diagram which shows the laminated constitution of the laminated | multilayer film for mold release of 3rd Embodiment.

4 is an explanatory view showing the action of the laminate film for release in press molding.

5 is a diagram showing a press-molding apparatus used in the embodiment.

Explanation of the sign

100A to 100L: Laminated Film for Release

10: layer made of modified polyolefin resin

20: layer made of adhesive fluororesin

30: layer made of polyolefin resin

40: layer made of fluororesin

50: core layer

60: middle layer

70: layer made of fluorine resin

200, 300: laminated press forming apparatus

Claims (27)

A laminated film for release having a layer made of a modified polyolefin resin and a layer made of an adhesive fluororesin laminated on at least one side of the layer. The release film for release according to claim 1, wherein a layer made of an adhesive fluororesin is laminated on both sides of the layer made of a modified polyolefin resin. The release film according to claim 1 or 2, wherein the layer made of an adhesive fluororesin has a thickness of 1 to 15 µm and the layer made of a modified polyolefin resin has a thickness of 10 to 100 µm. The laminated | multilayer film for mold release of which the layer which consists of a modified polyolefin resin, and the layer which consists of adhesive fluororesins are laminated | stacked on at least one surface of the layer which consists of polyolefin resin in order. The release laminated film according to claim 4, wherein a layer made of a modified polyolefin resin and a layer made of an adhesive fluorine resin are sequentially laminated on both sides of the layer made of a polyolefin resin. The thickness of the layer which consists of adhesive fluorine resin is 1-15 micrometers, the layer which consists of modified polyolefin resin is 0.5-100 micrometers, and the thickness of the layer which consists of polyolefin resin is 10 Laminated film for release that is from 100㎛. A laminated film for release, wherein a layer made of an adhesive fluororesin and a layer made of a fluororesin are sequentially laminated on at least one side of a layer made of a modified polyolefin resin. The laminate film for release according to claim 7, wherein a layer made of an adhesive fluororesin and a layer made of a fluororesin are sequentially laminated on both sides of the layer made of a modified polyolefin resin. The thickness of the layer which consists of modified polyolefin resins of Claim 7 or 8 whose thickness of the layer which consists of fluororesins is 1-15 micrometers, the layer which is made of adhesive fluororesin is 0.5-15 micrometers, Laminated film for release that is from 100㎛. A laminate film for release, wherein a layer made of a modified polyolefin resin, a layer made of an adhesive fluorine resin, and a layer made of a fluorine resin are sequentially laminated on at least one side of the layer made of a polyolefin resin. The laminate film for release according to claim 10, wherein a layer made of a modified polyolefin resin, a layer made of an adhesive fluorine resin, and a layer made of a fluorine resin are sequentially laminated on both sides of the layer made of a polyolefin resin. The thickness of the layer made of fluororesin is 1-15 micrometers, the thickness of the layer made of adhesive fluororesin is 0.5-15 micrometers, and the thickness of the layer made of modified polyolefin resin is 0.5. The laminated film for mold release of 100-100 micrometers, and thickness of the layer which consists of polyolefin resin is 10-100 micrometers. The laminated film for release of any one of Claims 1-12 whose modified polyolefin resin which forms the layer which consists of a modified polyolefin resin is a modified polyethylene resin. The laminated film for release of any one of Claims 7-13 whose fluorine resin which forms the layer which consists of a fluororesin is an ethylene-tetrafluoroethylene copolymer. A laminated film for release having a layer made of a heat resistant resin and a layer made of a fluororesin laminated on at least one side of the layer. The release film for release according to claim 15, wherein a layer made of a fluororesin is laminated on both sides of the layer made of a heat resistant resin. The release film according to claim 15 or 16, wherein the layer made of a fluororesin has a thickness of 1 to 15 µm and the layer made of a heat resistant resin has a thickness of 10 to 150 µm. 18. The mold release agent according to any one of claims 15 to 17, wherein the fluorine resin forming the layer made of the fluorine resin is an ethylene-tetrafluoroethylene copolymer, a low melting point ethylene-tetrafluoroethylene copolymer, or a mixture thereof. Laminated film. The laminate film for release according to any one of claims 15 to 18, wherein the heat resistant resin forming the layer made of the heat resistant resin is any one of a polycarbonate, an ethylene-vinyl alcohol copolymer, and a polyamide. As a laminated | multilayer film arrange | positioned between a press board and a laminated body at the time of carrying out lamination press molding of the laminated body which laminated | stacked several board | substrates through an adhesive agent under heating, It is a laminated | multilayer film which has a layer which consists of a core layer and the adhesive fluororesin laminated | stacked on both surfaces of the said core layer, The laminated | multilayer film for mold release whose core layer is formed from resin which has a melting | fusing point lower than adhesive fluororesin. The laminate film for release according to claim 20, wherein the core layer is a layer made of a modified polyolefin resin. 22. At least one thermoplastic material according to claim 20 or 21, further selected from the group consisting of a modified polyolefin resin, an ethylene-vinyl alcohol copolymer (EVOH) and a polyamide, between the layer of adhesive fluorine resin and the core layer. Laminated film for release which has an intermediate | middle layer which consists of resin. The laminated film for release according to claim 21 or 22, wherein the modified polyolefin resin is modified polyethylene. The laminate film for release according to any one of claims 20 to 23, wherein the layer made of an adhesive fluororesin has a thickness of 5 to 20 µm. The polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) according to any one of claims 20 to 24, on the outer side of the layer made of adhesive fluororesin. Tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), polychlorotrifluoroethylene (CTFE), ethylene-tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polyvinyl A laminated film for release having a layer made of a fluorine resin composed of at least one resin selected from the group consisting of fluoride and acid-modified ETFE (EFEP). The laminated film for release according to any one of claims 20 to 25, wherein the entire film has a thickness of 100 to 1200 µm. The laminate film for release according to any one of claims 1 to 26, which is formed by coextrusion.

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